Reduced phosphomolybdic acids wherein the average valence of the molybdenum is not more than 4



United States Patent REDUCED PHOSPHOMOLYBDIC ACIDS WHEREIN THE AVERAGE VALENCE OF THE MOLYB- DENUM IS NOT MORE THAN 4 Herrick R. Arnold, Frank S. Fawcett, and Walter W. Gilbert, Wilmington, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 19, 1955 Serial No. 529,575

6 Claims. (Cl. 23-139) This invention relates to new compositions of matter, to their preparation and to their use as catalysts. More particularly, this invention relates to novel catalytic compositions, to methods for their preparation and to their use as catalysts for the hydrogenation of carbon monoxide to high molecular weight, normally solid hydrocarbons.

This application is a continuation-in-part of our copending patent application Serial No. 368,487, filed July 16, 1953, now Patent Number 2,825,704.

Phosphomolybdic acids and their ammonium salts are commercially available products. It has been found that if these phosphomolybdic acids and ammonium phosphomolybdates are reduced under rigidly controlled conditions there are obtained novel compositions which possess unique catalytic properties for the hydrogenation of carbon monoxide to high molecular weight, normally solid, hydrocarbons.

It is an object of this invention to provide novel phosphomolybdic compounds and a method for their preparation. A further object is to provide a novel catalytic process for converting carbon monoxide to normally solid, high molecular weight, hydrocarbon polymers. Another object is to provide novel phosphomolybdic compounds which are effective as catalysts in the hydrogenation of carbon monoxide at relatively low pressures to normally solid, high molecular weight, polymethylenes. Other objects will appear hereinafter.

These objects are accomplished in accordance with the present invention by providing novel phosphomolybdic compounds represented by the formula P Mo O These phosphomolybdic compounds are the products obtained by reducing phosphomolybdic acids or their ammonium salts under selected and controlled conditions. It has now been discovered that reduced products corresponding in chemical composition to P Mo O are obtained by reducing phosphomolybdic acids or their ammonium salts at temperatures within the range of 350 to 600 C., during a to 60-hour reduction period with hydrogen at a space velocity of 500 to 1500 reciprocal hours.

This invention also includes the use of the above reduced phosphomolybdic compositions as catalysts for the hydrogenation of carbon monoxide to normally solid, high molecular weight hydrocarbons by heating and reacting carbon monoxide and hydrogen at a temperature of 125 to 350 C. under a pressure of at least 10 atmospheres in contact with a catalytic amount of a reduced phosphomolybdic composition corresponding to the formula P2MO2O 24O2 60.

The phosphomolybdic acids used as starting materials for preparation of the reduced phosphomolybdic compounds of this invention are commercially available materials and contain phosphorus to molybdenum ratios of 1:10 to 1:12.- Other phosphomolybdic acids containing phosphorus to molybdenum ratios outside this range, for example, those in which this ratio is as low as 1:2.5 give reduced products in accord with this invention. The ammonium salts of these phosphomolybdic acids are made by methods well known to those skilled in the art and can be used as equivalent starting materials for the acids. v Y "In producing the reduced phosphomolybdic acids and reduced ammonium phosphomolybdates, the phosphomolybdic acid or its ammonium salt employed as the starting material is placed in a heat-resistant glass, tube mounted within an electric furnace, and hydrogenalone, or hydrogen admixed with a diluent gas, such as nitrogen or carbon monoxide, is passed over the charge at -at mospheric pressure at a rate cormresponding to a space velocity which is desirably inexcess of 500 reciprocal hours, while the temperatureis raised from room temperature to above 350 C. at the rate of 50 to C. per hour. The reduction is continued under these conditions within the range of 350 C. to 600 C. for at least five hours. Thereafter the charge is permitted to cool to room temperature 'in non-oxidizing atmosphere, flushed at room temperature with nitrogen, and thereduced phosphomolybdic acid is stored under nitrogen, helium, or other inert gas.

The composition of the reduced phosphomolybdic sieve Range.

EXAMPLE I Commercial, analytical grade phosphomolybdic acid of composition by analysis corresponding to the formula 2(H PO ).22MoO .49H O was dehydrated to constant weight by heating at 200 C. The theoretical yield of anhydride assuming the reaction 7 is 77%. Actual yields varied Within the limits 7778%. The anhydride was hygroscopic and was stored in tightly sealed containers.

One hundred milliliters (ca. -170 g.) of the anhydrous granular phosphomolybdic acid was placed in a 45 mm. Pyrex tube, 34 inches long, with ground glass fittings on each end providing for a hydrogen inlet and exit, and a Pyrex thermocouple well penetrating through the catalyst bed. The catalyst rested on a plugof Pyrex glass wool. The reduction tube was placed in a splittype furnace, 18 inches long mounted at an angle of about 10 from horizontal.

Standard cylinder hydrogen was'passed first through activated charcoal and then over copper at 400 C. to a drying train consisting of a series of anhydrous calcium sulfate towers, followed by P 0 driers, and then to the reduction tube. The hydrogen passed through the catalyst bed at a space velocity of 1000 hrsf and thence to a condenser and dryer arranged to collectand measure water formed during reduction. Hydrogen flow was started at room temperature and the furnace was heated As reduction proceeded, the catalyst passed through a series of visible color changes starting from yellow at room temperature, changingto dark green about 250 C., to deep blue around. 350 C., and finally to black at 400 C. Water formed during reduction did not appear in significant amounts below 400 C.

The black, pyrophoric, reduced phosphornolybdic acid analyzed 73.37, 75.27% molybdenum and 2.10, 2.06% phosphorus, was amorphous to X-rays, and had-a surface area of 195 sq. m./g. Its average composition corressponded to P Mo O EXAMPLE [I Example I was repeated, except that the reduction was effected at 500 C. for 24 hours. The pyrophoric product analyzed 80.75% molybdenum and 2.34% phosphorus. Its average composition corresponded to P2MO22027.

EXAMPLE III One hundred seventy-five grams (ca. 160 cc.) of yellow crystalline phosphomolybdic acid, corresponding in composition to P O' .22MoO .56I-I' O, was placed in a heatresistant glass tube mounted in an electric furnace. Hydrogen at the rated 160 liters per hour, equivalent to a space velocity of 1000 hrswas passed through the tube at essentially atmospheric pressure. The system was then heated up from room temperature to 400 C. at the rate of about 75 to 80 C. per hour, and held under these conditions for 19 hours. During the heating up period in the temperature range of 100 to 200 C. the water of crystallization was removed, the acid turning light green at this point. In the interval 200 to 350 C. no further water was removed and no significant change in appearance was noted. At about 375 C. reduction started and was accompanied by evolution of water, and a gradual change in color from light green to deep blue and finally to black. occurred. After reduction for 19 hours, the product was. cooled. to room temperature in hydrogen, flushed at room temperature with nitrogen, discharged and sealed under nitrogen.

The black reduced, pyrophoric product analyzed 75.70, 75.53% molybdenum and 2.18, 2.22% phosphorus, which corresponds to P Mo O It had a surface area of 157 sq.m./ g. The X-ray diffraction pattern of this black reduced product indicated that it was essentially amorphous.

EXAMPLE IV A, sample of the phosphomolybdic acid, described and employed in Example, III as, the starting material, was first dehydrated by heating to. constant weight at 200 C. The anhydrous powder was then reduced in hydrogen for 18 hours at 400 C. under the conditions described in Example III. The reduced product was black, pyrophoric, and substantially amorphous to X-rays. Elementary analysis showed the product to contain 71.51, 71.57%

molybdenum and 2.16, 2.17% phosphorus, which cor- I responds to P2M021047.

Ammonium phosphomolybdate (NH P Mo O was precipitated at a pH of 1 to 2 from a 10% aqueous solution of phosphomolybdic acid by the addition of 28% aqueous ammonia. The ammonium salt so prepared was reduced at'atmospheric presure and 400 C. in hydrogen 4 at a space velocity of 1000 reciprocal hours for 24 hours. The reduced product corresponded in composition to P Mo O and was black, amorphous to X-rays, pyrophoric, and had a surface area of 233 sq.m./ g.

EXAMPLE VII Example I was repeated, except that the reduction was effected by raising the temperature of the catalyst bed to 550 C. over a period of 23 hours and maintaining the temperature at 550 C. for 24 additional hours. The analysis of the steel gray, highly pyrophoric product was: 95.22% M0; 267% P; surface area, 51.3 sq. m./g., which corresponds to a composition P Mo O EXAMPLE VIII Example I was repeated, except that the temperature of reduction was raised to 600 C. over a period of 23 hours and maintained at 600 C. for 24 additional hours. The pyrophoric product had the following analysis: 95.89% Mo; 2.69% P; surface area, 35 sq. m./g., corresponding to the composition P Mo O EXAMPLE IX Example I was repeated, except that the time of reduction at 400 C. was 60 hours. The black, pyrophoric product had the following analysis: 74.95% Mo; 2.13% P; surface area, 151 sq. m./g., corresponding to a composition P Mo O EXAMPLE X Example I was repeated, except that the temperature of the reduction was 475 C. for 48 hours. The analysis of the pyrophoric product was as follows: 87.32% Mo; 2.37% P; surface area, 163 sq. m./g., corresponding to acomposition P2MO24O17.

The reduced phosphomolybdic acid and reduced ammonium phosphomolybdates of this invention are effective catalysts for hydrogenating carbon monoxide to high molecular weight, normally solid polymethylenes as illustrated by the following examples wherein inherent viscosity refers to measurements made at 0.1% concentration in tetrahydronaphthalene at C. All of these hydrogenations were effected in a 400 cc. reactor, except for Example XII in which a 190 cc. reactor was used.

EXAMPLE x1 A pressure reactor was charged with 100 cc. of xylene and 10 g. of a reduced phosphomolybdic acid prepared as in Example III (P Mo O The charge was then heated at 225 C. under 1000 atmospheres of 2:1 hydrogen/carbon monoxide mixed gas. During 15 hours a gas absorption of 285 atmospheres occurred. The crude reaction product contained hard lumps of solid, and, in addition, some fiufiy white polymer. The mixture was filtered and dried. The product was then extracted with benzene, yielding a trace of solid material. Further extraction with boiling xylene, followed by dilution of the extract with methanol, yielded 2.0 g. of fibrous white solid polymer having an inherent viscosity of 2.76 and a melting point of 127 to 132 C. This polymer was manually spun to give fibers which could be cold drawn, It was compression molded at 190 C. to give colorless transparent films which were flexible, stiff, and tough.

The above experiment was repeated using the reduced phosphomolybdic acid of Example IV (P2MO21O47), as the catalyst. Under these conditions the pressure drop amounted to atmospheres. After extraction of the product with benzene, to remove traces of soluble'material, the residue was extracted with boiling xylene and on dilution of the extract with methanol there was obtained 1.52 g. of a white solid polymethylene having an 1 EXAMPLE XII A mixture of 50 cc. of xylene and 11 g. of the reduced phosphomolybdic acid of Example IV A mixture of 100 cc. of water and 13 g. of the reduced phosphomolybdic acidof Example IV (P Mo O was heated at 275 C. for hours under a 2:1 hydrogen/ carbon monoxide gas pressure of 1000 atmospheres. Benzene extraction to remove soluble material, followed by extraction of theresidue with boiling xylene and dilution of the extract with methanol, gave 2.70 g. of a polymethylene.

EXAMPLE IV A mixture of 100 cc. of xylene, 1 g. of anhydrous ammonia, and 11.6 g. of the reduced phosphomolybdic acid of Example IV (P Mo O was heated at 275 C. under a 2:1 hydrogen/carbon monoxide mixed gas pressure of 1000 atmospheres. After 15 hours the gas absorption corresponded to a pressure drop of 565 atmospheres. Benzene extraction of the product to remove soluble material, followed by extraction with boiling xylene and dilution of the extract with methanol yielded 1.91 g. of white solid polymer.

EXAMPLE XV A mixture of n-propyl alcohol, 5 g. of anhydrous potassium carbonate, and 21.3 g. of the reduced phosphomolybdic acid of Example IV (P Mo O were heated at 275 C. for 15 hours under 1000 atmospheres of 2:1 hydrogen/carbon monoxide mixed gas. -The crude reaction product was separated into a solidand a liquid portion by filtration. The solid was extracted with boiling benzene and on evaporation of the extract there was obtained 1.3 g. of a brown wax. This wax analyzed:

Analysis.Calcd for (CH C, 85.70; H, 14.30. Found: C, 83. 2; H, 14.09.

Further extraction of the benzene insoluble portion with boiling xylene, followed by dilution with methanol yielded 5.43 g. of a polymethylene having an inherent viscosity of 1.04. This product analyzed 85.23% C, and 14.66% H.

Distillation of the crude liquid fraction gave 24 g. of material boiling in the range of 69 to 82 C. and 5.8 g. of residue boiling higher than n-propyl alcohol.

EXAMPLE XVI" A mixture of 100 cc. of xylene and 14.5 g. of the reduced phosphomolybdic acid of Example V (P Mo O was heated at 275 C. under a 2:1 hydrogen/carbon boiling xylene gave 1.72 g. of a polymethylene.

EXAMPLE XVII A mixture of 100 cc. of xylene and 35 g. of the reduced ammoniumphosphomolybdate of Example VI "(P Mo O was heated at 275 C. under a 2:1 bydrogen/carbon monoxide mixed gas pressure of 1000 atmospheres. During a 9.75-hour reaction time the pressure drop corresponded to 810 atmospheres. After extraction of the solid product with boiling benzene to remove soluble material, the residue was extracted with boiling xylene to yield 5.86 g. of solid polymer having an inherent viscosity of 1.60.

EXAMPLE XVIII A mixture of 100 cc. of xylene and 4.8 g. of reduced phosphomolybdic acid of Example I (P Mo O was heated over a temperature range of 100-275 C. under a 1:1 hydrogen/carbon monoxide mixed gas pressure of 50-200 atmospheres for 12 hours. The total pressure drop during this period corresponded to 50 atmospheres. The solid product was extracted with boiling benzene for two days to remove 0.21 g. of waxy polymer, followed by extraction with boiling xylene to yield 1.06 g. of solid polymer having an inherent viscosity of 1.80.

EXAMPLE XIX A mixture of cc. of xylene and 7.0 g. of reduced phosphomolybdic acid, prepared according to Example I (P Mo O was heated at 100-250 C; under 33.4 to atmospheres pressure of a 1:1 hydrogen/carbon monoxide mixed gas for 12- hours. The pressure drop during this period amounted to 49 atmospheres. The solid product was extracted with boiling benzene to remove a trace of waxy product, and with boiling xylene to yield 0.75 g. or" high molecular weight polymethylene, having an inherent viscosity of 2.31. a

This experiment was repeated at 200 C. and 167 atmospheres pressure. There was obtained 0.44 g. of polymethylene of inherent viscosity 2.58.

Repetition of the above experiment at 50 and 33 atmospheres, yielded high molecular weight polymethylenes, thus showing that these catalyst compositions are active even under mild conditions.

EXAMPLE XX The preparation of Example XVIII was repeated, except that the conditions of operation were 275 C. and 71.7 to 111.7 atmospheres pressure. There were obtained high molecular weight polymethylene, 0.40 g.,

having an inherent viscosity of 1.85, and a slight trace of wax.

EXAMPLE XXI EXAMPLE XXII The preparation of Example XVIII was repeated, except that the hydrogen/carbon monoxide mixed gas was in the ratio of 1:2. There was obtained 1.21 g. of solid polymethylene exhibiting an inherent viscosity of 1.47.

EXAMPLE XXIII The preparation of Example XVIII was repeated, except that the hydrogen/ carbon monoxide mixed gas was in the ratio of 1:3. There was obtained 0.89 g. of solid polymethylene of inherent viscosity of 1.43.

EXAMPLE XXIV The preparation of Example XIX was repeated, employing a catalyst of composition corresponding to P Mo O (Example X). The solid product comprised a trace of wax and 0.23 g. of high molecular weight polymethylene.

EXAMPLE XXV A mixture of 100 cc. of xylene, 5.1 g. of a catalyst composition corresponding to P Mo O (Example VIII) was heated at 245-275 C. under a 1:1 hydrogen/carbon monoxide gas pressure of 8501'000atmospheres. During a 12-hour reaction period there was an observed pressure drop of"7 87 atmospheres. The product consisted of 1.33 g. of waxy solid and 1.36 g. of highmolecular weight, xylene-extracted polymer.

EXAMPLE XXVI w herein x is zero through 12 and y is zero through 10. In the reduction, the ammonium salts behave essentially the same as the free acids. The products obtained by reducing the ammonium salts show by analysis only a very small amount of nitrogen, e.g., of the order of about 1%.

In the reduction, hydrogen alone or hydrogen admixed with a diluent gas, e.g., nitrogen or carbon monoxide, is permitted to pass at atmospheric pressure over the heated phosphomolybdic acid or ammonium salt (not metal) at a space velocity which is at least 500 hI'S. Usually the space velocity is between 700 and 1100 hrsbecause under these conditions good reduction rates, under the preferred temperature conditions, are realized.

The reduction is effected at atmospheric pressure with hydrogen alone or with hydrogen admixed with a diluent gas such as nitrogen or carbon monoxide at a temperature which is at least 350 C. and usually above 375 C. but not more than 600 C. As a rule, however, the reduction is effected at 400 to 550 C.

The reduction is conducted until the average valence of the molybdenum as determined by permanganate titration is not more than 4 as in Example IV or less than 4 as in the other examples. The time required to effect this depends upon the composition of the reducing gas and the temperature used. As a rule it is at least 5 hours but not more than about 60 hours. Under the preferred operating temperature conditions of 400475 C., and with hydrogen alone as the reducing gas, the time of reduction generally will be between 18 and 40 hours.

The composition of the reduced phosphomolybdic acid corresponds to P M O wherein the average valence of the molybdenum is not more than 4. Within the preferred operating temperature range of 400-475 C. and an 18-40 hour reduction time, the reduced phosphomolybdic acids will correspond to P Mo O With longer periods of reduction up to 60 hours or higher temperatures up to 600 C., the reduced phosphomolybdic acids will correspond to P Mo O The hydrogenation of carbon monoxide can be carried out as a batch operation, or as a semi-continuous, or as a continuous upfiow, down-flow, or counter-current operation. It can also be carried out co-currently or as a boiling bed or fluidized catalyst operation.

The mole ratio of hydrogen to carbon monoxide in the gas mixture may vary from :1 to 1:10. Usually mole ratios of from 3:1 to 1:2 are used because gas mixtures in this range of composition are ordinarily available in large scale and give optimum results from the standpoint of desired high molecular weight hydrocarbon polymer.

The temperature at which the hydrogenation of the carbon monoxide is elfected. lies in the range of 125 to 350 C. Because good reaction rates with best yields of desired high molecular weight hydrocarbons are ob tained in the range of 150 to 275 C., this range em- .braces the preferred operating temperature conditions.

The hydrogenation of the carbon monoxide is effected under a total pressure which is atleast 10 atmospheres. Because better yields of desired high molecular weight hydrocarbons, with maximum utilization of the carbon monoxide and hydrogen is obtained employing pressures in excess of 30 atmospheres, the use of such pressure is economical and constitutes a preferred mode of operation. The maximum pressure which-may be used is dictated by the mechanical limitations of the equipment used. For practical reasons, pressures above 5000 atmos pheres are generally not used and this constitutes a practical upper limit of pressure.

Because the reaction is highly exothermic, it is'pre ferred to operate in the presence of a liquid reaction medium, which besides aiding in. the dissipation of the heat of reaction also functions'to bring about better catalyst contact, and hence improves the efficiency of the process. Suitable media are water and such organic compounds as cyclohexane, methanol, propanol, decahydronaphthalene, tetrahydronaphthalene, benzene, tolu-. ene, xylene, cyclohexanone, methyl isobutyl ketone, etc.

The reaction medium can occupy up to 60% or as little as 5% of the reactor'volurne. Generally, however, in batch operation the reaction medium occupies between 25% and 50% of the reactor volume.

The time of reaction depends upon such interdependent variables as temperature, pressure, and amount and type of catalyst used. Under preferred conditions for batch operation, the reaction reaches essential completion in from 3 to 20 hours.

The amount of catalyst used depends upon the temperature and pressure used, the method of operation selected, catalyst activity, etc. As a rule in batch operation it will be between 1.5 and 30%, and preferably between 2.5 and 20% by weight of the reaction medium. In continuous operation, the weight of product in the reaction at any one time is ordinarily less than the weight of catalyst, but the total weight of material processed during the active life of the catalyst is usually at least 10 times the catalyst weight.

The surface of the reactor in contact with the reactants appears to be a factor in determining the molecular weight and yield of high molecular weight hydrocarbons obtained from carbon monoxide. Silver and stainless steel are satisfactory materials.

The catalysts of this invention make it possible to convert carbon monoxide to normally solid, high molec ular weight hydrocarbons having properties which make them outstandingly useful for conversion to films and fibers. In the table below are summarized the physical properties of these products determined on composite samples synthesized at 225 C. and 275 C. In the table TS refers to tensile strength in p.s.i., and elong. to elongation at break in percent.

Table Synthesis temperature 225 0. 275 C.

Inherent viscosity r 2. 8 1. 6 Density 0. 97 0. -0. 96 20-mil film, 'IS/elong. (p.s.i. percent) 3. 500/622 3, 750/50 5-r ml film, TSjelong. (psi. percent) 3, 775/ 3, 900/33 Stlfil'lGSS, p.S.1 122, 000 130, 000

As many apparently widely different embodiments of 'this invention may be made without departing from the I a zz sa- 9 3. Phosphomolybdic acid represented by the formula 2,599,326 P2MO24017. 4. Phosphomolybdic acid represented by the formula 2,714,583 P2MO21O47. 5. Phosphomolybdic acid represented by the formula 5 2,749,318 P2MO22O42.

6. Phosphomolybdic acid from the class represented by the formula P2MO20 24O2 37 and wherein the average valence of the molybdenum is not more than 4.

2,503,991 Bechtold Apr. 11, 1950 10 Theoretical 10 Gruen June 3, 1952 Farlow Sept. 15, 1953 Fawcett Aug. 2, 1955 Arnold Dec. 6, 1955 Osthotf June 5, 1956 Arnold et a1. Apr. 9, 1957 OTHER REFERENCES Mellor: Comprehensive Treatise on Inorganic and Chemistry, Longmans, Green and Co., New York, 1923, vol. 11, pages 660 and 661.

Hoffman: Lexikon der Anorganischen Verbinsungen, Band II, Nos. 56-81, page 708 (1912-1914). 

1. PHOSPHOMOLYBDIC ACID FROM THE CALSS REPRESENTED BY THE FORMULA P2MO20-2402-60 AND WHEREIN THE AVERAGE VALENCE OF THE MOLYBDENUM IS NOT MORE THAN
 4. 